Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/22—Polybenzoxazoles
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
  • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds

Definitions

• the present invention relates to positive photosensitive resin compositions.
• the present invention relates to positive-working, aqueous base developable photosensitive polybenzoxazole (PBO) precursor compositions that are suitable for applications in the field of microelectronics.
• PBO polybenzoxazole
• polymers that demonstrate high temperature resistance are generally well known.
• Precursors of such polymers such as polyimides and polybenzoxazoles can be made photoreactive with suitable additives.
• the precursors are converted to the desired polymer by known techniques such as exposure to high temperatures.
• the polymer precursors are used to prepare protective layers, insulating layers, and relief structures of highly heat-resistant polymers.
• PBO photosensitive polybenzoxazoles
• the diazoquinone compound inhibits the solubility of the PBO precursor in an aqueous base. After exposure to light, the diazoquinone compound undergoes photolysis and converts to indenecarboxylic acid, which promotes the aqueous base solubility of the PBO precursor.
• the present invention provides a positive photosensitive resin composition containing a silane diol such as diarylsilane diol or dialkylsilane diol, one or more capped polybenzoxazole precursors, a photosensitive agent (e.g. diazoquinone compound, dihydropyridine, or mixtures thereof), and a solvent.
• a silane diol compound is an essential component of the positive acting, photoactive resin composition.
• the silane diol surprisingly acts as a dissolution inhibitor. This behavior is contrary to what one would expect, since in other systems such as those described in U.S. Patent No. 5,856,065, a silane diol functions as a dissolution enhancer.
• the present invention provides a positive photosensitive resin composition
• a positive photosensitive resin composition comprising a silane diol, one or more capped polybenzoxazole precursors, a photosensitive agent, and a solvent.
• the composition of the present invention exhibits several improvements over prior art compositions. For example, dissolution inhibition and crack resistance are noticeably improved. Furthermore, there is a decrease in swelling and skinning during exposure to aqueous developers, as compared to other compositions at a similar inhibition level. These improvements allow longer, more controlled development times resulting in increased develop process latitude.
• the silane diol compound can be. for example, a diarylsilane diol or a dialkylsilane diol. Most preferred is a diphenylsilane diol.
• the silane diol is included in the composition at about 0.1 wt. % to 10.0 wt. %. preferably at about 0.5 wt. % to 7.5 wt. %, and most preferably at about 1 wt. % to 5 wt. %.
• One or more capped polybenzoxazole precursor polymers are formed by the reaction of a polybenzoxazole precursor (G) with a diazoquinone compound.
• the polybenzoxazole precursor has a polymerization degree of 10 - 1000 and is synthesized by the reaction of monomers (A), (B), and (C) in the presence of a base:
• x is 10 to 1000, and y is 0 to 900;
• Arj is a tetravalent aromatic, aliphatic, or heterocyclic group;
• Ar 2 is a divalent aromatic, heterocyclic. alicyclic or aliphatic group;
• Ar 3 is a divalent aromatic, aliphatic or heterocyclic group, and W is Cl, OR and H; wherein R is -CH 3 , -C 2 H 5 , n-C 3 H 7 , i-C 3 H 7 , «-C 4 H 9 , t-C 4 H 9 , cyclohexyl. and the like.
• the ratio of [(A) + (B)]/(C) is generally between about 0.9 to 1.1.
• Monomer (A) is about 10 - 100 mole % of [(A) + (B)] and monomer (B) is about 0
• Arj is a tetravalent aromatic, aliphatic, or heterocyclic group, and can include the following moieties:
• Xi is O -C(CF 3 ) 2 -CH, -SO,
• - ⁇ HCO or -Si - R is alkyl or cycloakyL such as
• monomer (A) may be a mixture of two or more monomers.
• Ar? is a divalent aromatic, heterocyclic. alicyclic, or aliphatic group that may or may not contain silicon.
• the Ar 2 containing monomer (B) includes, for example, 5(6)-diamino-l-(4-aminophenyl)-1.3.3-trimethylindane (DAPI). m- phenylenediamine, -phenylenediamine. 2.2'-bis(trifluoromethyl)-4,4 , -diamino- l,l '-biphenyl, 3,4'-diaminodiphenyl ether.
• DAPI 5(6)-diamino-l-(4-aminophenyl)-1.3.3-trimethylindane
• Ar 3 is a divalent aromatic or heterocyclic group, and includes, for example:
• X 2 is -O-, -S-, -C(CF 3 ) 2 -, -CH 2 -, -SO 2 -, or -NHCO-.
• Ar 3 is not restricted to these groups.
• monomer (C) may be a mixture of two or more monomers.
• the diazoquinone compound that is combined with the PBO precursor (G) can be one of the following:
• the preferred reaction solvents are N-methyl-2-pyrrolidone (NMP), ⁇ - butyrolactone (GBL). N.N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl-2-piperidone. dimethylsulfoxide (DMSO), sulfolane. and diglyme. Most preferred are N-methyl-2-pyrrolidone (NMP) and ⁇ - butyrolactone (GBL).
• Any suitable reaction for reacting such dicarboxylic acid or its dichloride or diester with at least one aromatic and/or heterocyclic dihydroxydiamine, and optionally, with at least one diamine may be used. Generally, the reaction is carried out at about 10 °C to about 50 °C for about 6 to 48 hours. The molar ratio of diacid to (diamine + dihydroxydiamine) should be about 0.9 - 1.1 :1.
• the capped PBO precursor can be prepared according to the following reaction.
• any suitable method for reacting a polybenzoxazole with the photoactive moiety Cl-SO 2 -Z may be used. Generally, the reaction is carried out at about -10 °C to about 30 °C for about 3 to 24 hours in the presence of a base such as pyridine. trialkylamine. methylpyridine. lutidine, n-methylmorpholine. and the like. The most preferred base is triethylamine.
• the ratio of b/x is from 0.01 to 0.35. The more preferred b/x ratio is from 0.02 to 0.20 and most preferred is from 0.03 to 0.05.
• the reaction mixture should be protected from actinic rays.
• the positive photosensitive resin composition includes one or more capped polybenzoxazole precursors at about 10 wt. % to 50 wt. %. Preferably, about 20 wt. % to 45 wt. %, and most preferably, about 30 wt. % to 40 wt. % of the capped polybenzoxazole precursor is added.
• the photosensitive agent consists of a diazoquinone compound (H), dihydropyridine compound (I), or mixtures thereof.
• Suitable diazoquinone compounds can be, but are not limited to, one of the following structures:
• D independently can be H or one of the following moieties:
• the dihydropyridine (I) can be, for example, a compound with the following structure:
• R groups are the same or different and have the following structure:
• R is H. C
• the dihydropyridine may be:
• Y is -OR 2 where R is a monovalent substituted or unsubstituted aromatic group or aliphatic group. CN, Cl, Br, or
• Capped polybenzoxazole precursor (F) can be formulated with one or more diazoquinone compounds (H), one or more dihydropyridines (I), or mixtures thereof.
• the diazoquinone compound (H) used in this composition is about 1 wt.% to 20 wt.% of the total weight of the composition, preferably, about 2 wt. % to 10 wt. %, and most preferably, about 3 wt. % to 5 wt. %.
• the amount of dihydropyridine compound (I) used in this composition is about 1 wt. % to 20 wt. % of the total weight of the composition, preferably, about 2 wt. % to 10 wt.
• the amount of (H) + (I) in this composition is about 1 wt. % to 20 wt. % of the total weight of the composition, preferably, about 2 wt. % to 10 wt. %, and most preferably, about 3 wt. % to 5 wt. %.
• the positive acting, photoactive resin of this invention is used in a solution dissolved in a solvent.
• suitable solvents include, but are not limited to organic solvents, such as N-methylpyrrolidone (NMP), ⁇ - butyrolactone (GBL), N,N- dimethylacetamide (DMAc), dimethyl-2-piperidone, N,N-dimethylformamide (DMF), and mixtures thereof.
• NMP N-methylpyrrolidone
• GBL ⁇ - butyrolactone
• DMAc N,N- dimethylacetamide
• DMF dimethyl-2-piperidone
• DMF N,N-dimethylformamide
• the present invention may further include additives.
• Suitable additives are. for example, adhesion promoters such as amino silanes. leveling agents, mixtures thereof, and the like.
• the present invention includes a process for forming a relief pattern.
• the process comprises the steps of: (a) coating on a suitable substrate, a positive-working photosensitive composition comprising a silane diol, one or more capped polybenzoxazole precursors having the structure (F), a photosensitive agent, and a solvent, thereby forming a coated substrate; (b) exposing the coated substrate to actinic radiation; (c) post exposure baking the coated substrate at an elevated temperature; (d) developing the coated substrate with an aqueous developer, thereby forming a developed substrate; (e) rinsing the developed substrate: and (e) baking the rinsed substrate at an elevated temperature, thereby- curing the relief pattern.
• the positive acting, photoactive resin of this invention is coated on a suitable substrate such as a silicon wafer, a ceramic substrate, or the like.
• Coating methods include, but are not limited to spray coating, spin coating, offset printing, roller coating, screen printing, extrusion coating, meniscus coating, curtain coating, and immersion coating.
• the resulting film may optionally be prebaked at an elevated temperature of about 70-120°C for several minutes to half an hour, depending on the method, to evaporate the remaining solvent.
• the resulting dry film is exposed to actinic rays in a preferred pattern through a mask.
• actinic rays X-rays, electron beam, ultraviolet rays, visible light, and the like can be used as actinic rays.
• the most preferable rays are those with wavelength of 436 nm (g- line) and 365 nm (i-line).
• the coated substrate Following exposure to actinic radiation, it is advantageous to heat the coated substrate to a temperature between about 70° C and 120° C.
• the coated substrate is heated in this temperature range for a short period of time, typically several seconds to several minutes. This process step is commonly referred to in the art as post exposure baking.
• the film is developed by an aqueous developer and a relief pattern is obtained.
• the aqueous developer includes the solution of alkalis such as an inorganic alkali (e.g., potassium hydroxide, sodium hydroxide, ammonia water), primary amines (e.g., ethylamine, n-propylamine), secondary amines (e.g. diethylamine, di-fl-propylamine), tertiary amines (e.g., triethylamine), alcoholamines (e.g.
• an inorganic alkali e.g., potassium hydroxide, sodium hydroxide, ammonia water
• primary amines e.g., ethylamine, n-propylamine
• secondary amines e.g. diethylamine, di-fl-propylamine
• tertiary amines e.g., triethylamine
• alcoholamines e.
• triethanolamine triethanolamine
• quaternary ammonium salts e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide
• TMAH tetramethylammonium hydroxide
• An appropriate amount of a surfactant can be added to the developer. Development can be carried out by means of immersion, spray, puddling, or other similar developing methods.
• the relief pattern is then rinsed using deionized water.
• the oxazole ring is then formed by curing of the relief pattern to obtain the final pattern of high heat resistant polymer. Curing is performed by baking the developed substrate at the glass transition temperature T g of the polymer to obtain the oxazole ring that forms a final pattern of high heat resistance.
• the yield was almost quantitative and the inherent viscosity of the polymer was 0.24 dL/g measured in NMP at a concentration of 0.5 g/dL at 25° C.
• Synthesis Example B To a 2 L, three-necked, round bottom flask equipped with a mechanical stirrer, 200 g (370 mmol) of the polymer obtained from Synthesis Example A and 1000 mL of tetrahydrofuran (THF) were added. The mixture was stirred for 30 minutes and the solid was fully dissolved. Then 3.0 g (1 1.3 mmol) of 2,1- naphtoquinonediazide-5-sulfonic chloride was added and the mixture was stirred for another 30 minutes. Next, 1.36 g (13.6 mmol) triethylamine was added gradually over a period of 45 minutes and the reaction mixture was stirred for 5 hours.
• THF tetrahydrofuran
• the formulation of the following composition was prepared by combining 28.1 wt. % of the PBO precursor of Synthesis Example B, 3.34 wt. % photoactive compound (PAC), 0.28 wt. % adhesion promoter, and 2.81 wt. % diphenylsilane diol dissolved in 65.47 wt. % GBL solvent to obtain a photosensitive resin composition.
• PAC photoactive compound
• 0.28 wt. % adhesion promoter 0.28 wt. % adhesion promoter
• 2.81 wt. % diphenylsilane diol dissolved in 65.47 wt. % GBL solvent
• composition was then spin coated onto a silicon wafer and baked on a hotplate for 3 min at 120° C to obtain a film of about lO ⁇ m thick.
• This film was exposed on an i-line stepper and developed for 50s using a 0.262N aqueous TMAH solution followed by a DI water rinse.
• the formulation of the following composition was prepared by combining 28.1wt. % of the PBO precursor of Synthesis Example B, 3.34 wt. % PAC, 0.28 wt. % adhesion promoter, and 2.81 wt. % diphenylsilane diol dissolved in 65.47 wt. % GBL solvent to obtain a photosensitive resin composition.
• composition was then spin coated onto a silicon wafer and baked on a hotplate for 3 min at 120° C to obtain a film of about 10.5 ⁇ m thick.
• This film was exposed on an i-line stepper and developed for 70s using a 0.262N aqueous TMAH solution followed by a DI water rinse.
• Example 3 The formulation of the following composition was prepared by combining
• composition was then spin coated onto a silicon wafer and baked on a hotplate for 3 min at 120° C to obtain a film of about 10.5 ⁇ m thick.
• This film was exposed on an i-line stepper and developed for 70s using a 0.28N aqueous TMAH solution followed by a DI water rinse. A resolution of 2 ⁇ m was obtained at 560 mJ/cm 2 with a film retention of 75.2%. No cracking, peeling, or skinning was observed.
• Example 4 The formulation of the following composition was prepared by combining 28.1 wt. % of the PBO precursor of Synthesis Example B. 3.34 wt. % PAC, 0.28 wt. % adhesion promoter, and 2.81 wt. % diphenylsilane diol dissolved in 65.47 wt. % GBL solvent to obtain a photosensitive resin composition.
• composition was then spin coated onto a silicon wafer and baked on a hotplate for 3 min at 120° C to obtain a film of about 10.5 ⁇ m thick.
• This film was exposed on an i-line stepper and developed for 60s using a 0.33N aqueous TMAH solution followed by a DI water rinse. A resolution of 2 ⁇ m was obtained at 460 mJ/cm 2 with a film retention of 71%. No cracking, peeling, or skinning was observed.
• Comparative Example 1 The formulation of the following composition was prepared by combining
• composition was then spin coated onto a silicon wafer and baked on a hotplate for 3 min at 120° C to obtain a film of about 9.8 ⁇ m thick.
• This film was exposed on an i-line stepper and developed for 60s using a 0.262N aqueous TMAH solution followed by a DI water rinse. Energy to clear was 260 mJ/cm 2 with a film retention of 54.8%>. Similar exposure to the developer of synthesis examples A and B, but the unexposed film was severely attacked.
• the formulation of the following composition was prepared by combining 28.91 wt. % of the PBO precursor of Synthesis Example B, 3.44 wt. % PAC, and 0.29 wt. % adhesion promoter dissolved in 67.36 wt. % GBL solvent to obtain a photosensitive resin composition.
• composition was then spin coated onto a silicon wafer and baked on a hotplate for 3 min at 120° C to obtain a film of about 9.9 ⁇ m thick.
• This film was exposed on an i-line stepper and developed for 30s using a 0.262N aqueous TMAH solution followed by a DI water rinse. Energy to clear was 820 mJ/cm with a film retention of 78.6%. No cracking, peeling, or skinning was observed.
• the formulation of the following composition was prepared by combining 28.91 wt. % of the PBO precursor of Synthesis Example B, 3.44 wt. % PAC, and 0.29 wt. % adhesion promoter dissolved in 67.36 wt. % GBL solvent to obtain a photosensitive resin composition.
• the formulation of the following composition was prepared by combining 28.9 wt. % of a PBO precursor at a slightly higher molecular weight with 0.5% w/w attached DNQ, 3.47 wt. % PAC, and 0.29 wt. % adhesion promoter dissolved in 67.34 wt. % GBL solvent to obtain a photosensitive resin composition.
• the composition was then spin coated onto a silicon wafer and baked on a hotplate for 3 min at 120° C to obtain a film of about 8.3 ⁇ m thick.
• the inhibition level of this composition is not as high as in examples 1 and 2 (which use the same developer), yet unlike these examples, this film exhibits signs of excessive swelling and stress caused by the develop process.

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